CN112048058B - Preparation method of high-melting-point crystalline biodegradable copolyester - Google Patents

Preparation method of high-melting-point crystalline biodegradable copolyester Download PDF

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CN112048058B
CN112048058B CN202010807847.6A CN202010807847A CN112048058B CN 112048058 B CN112048058 B CN 112048058B CN 202010807847 A CN202010807847 A CN 202010807847A CN 112048058 B CN112048058 B CN 112048058B
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isohexide
polyester prepolymer
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dibasic acid
acid
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CN112048058A (en
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王华平
乌婧
陈咏
林一鸣
张旭
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Donghua University
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Abstract

The invention relates to a preparation method of high-melting-point crystalline biodegradable copolyester, which comprises the steps of mixing isohexide-based polyester prepolymer, aliphatic polyester prepolymer and chain extender, and reacting to prepare high-melting-point crystalline biodegradable copolyester, wherein the isohexide-based polyester prepolymer is prepared by reacting isohexide with dibasic acid or dibasic acid ester; the aliphatic polyester prepolymer is one or more of a PBS prepolymer, a PCL prepolymer, a PIsS prepolymer, a PBST prepolymer and a PBAT prepolymer; the mass ratio of the isohexol-based polyester prepolymer to the aliphatic polyester prepolymer is 2: 8-9: 1; the prepared high-melting-point crystalline biodegradable copolyester has the number average molecular weight of 10,000-60,000 g/mol, the intrinsic viscosity of 0.5-1.2 dL/g and the melting point of 150-190 ℃, and is suitable for preparing non-woven materials such as fibers, spun-bonded fabrics, non-woven fabrics and the like.

Description

Preparation method of high-melting-point crystalline biodegradable copolyester
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and relates to a preparation method of high-melting-point crystalline biodegradable copolyester.
Background
Along with the improvement of the living and medical level of people, the implementation of a two-stage policy and the acceleration of the aging process, the demand of disposable medical supplies in China shows a rapid growth trend. At present, the annual total consumption of women sanitary napkins, baby diapers and adult incontinence care products in China exceeds 1200 hundred million tablets, and the output value exceeds 1000 hundred million. When sudden public events such as natural disasters and epidemics occur, the demand of the products is increased explosively. The main component of the disposable medical and sanitary product is single-layer or multi-layer composite non-woven fabric prepared by taking synthetic macromolecules such as polypropylene, polyethylene terephthalate (PET) and the like as raw materials, the composite non-woven fabric is difficult to degrade, the service cycle is short, the abandonment speed is high, and the solid waste amount generated in China is at least 100 ten thousand tons every year. Therefore, the development of biodegradable disposable medical and sanitary products is an urgent problem with important practical significance and ecological value.
Biodegradable synthetic polymer suitable for non-woven processThe material should have certain crystallinity and melt spinning properties to meet the requirements of fiber formation and crystal orientation. At present, the main biodegradable polymers are mainly aliphatic polyesters, such as polylactic acid (PLA), Polycaprolactone (PCL), polybutylene succinate (PBS) and the like. Biodegradable polyesters can be classified into polyhydroxy acids and polydiacid diol esters according to the difference in the chemical structure of the monomers. Polylactic acid (PLA) is an important class of polyhydroxy acids, and has been widely studied in the field of fibers and nonwoven materials in recent years due to its good spinning properties. According to the difference of the addition ratio of D/L isomer of the synthesized monomer, PLA has a wider melting point range which is about 125-180 ℃. High melting PLA is obtained mainly by adding high proportions of D-type lactic acid or lactide monomer. The patent (CN107475808) discloses a preparation method of polylactic acid short fiber with a low-melting-point sheath-core structure, wherein a low-melting-point biodegradable sheath-core fiber is prepared from PLA slices with melting points of 125-135 ℃ and 155-170 ℃ respectively, and can be applied to the application field of non-woven fabrics. The PCL can be prepared from the cyclohexadene through ring-opening polymerization, the melting point (60 ℃) and the glass transition temperature (60 ℃) of the PCL are both low, and the application of the existing fiber is limited. The biodegradable polyester of the poly-dibasic acid and the dibasic acid ester is mainly prepared by melting and polymerizing dihydric alcohol and dibasic carboxylic acid. Compared with polyhydroxy acid, the dihydric alcohol and the dicarboxylic acid monomers are more abundant, and the polyester with wider material performance can be obtained by utilizing the combination copolymerization of different monomers. The currently known full-aliphatic polyesters have a low melting point due to their high flexibility of molecular structure. Wherein the PBS has the highest melting point (115 ℃) and the other types have the melting points of 40-100 ℃. Meanwhile, the polymer has weak intermolecular force and low tensile strength, and the application of the fiber is greatly limited. In order to improve the thermal and mechanical properties of PBS-based polyesters, it is common to copolymerize with rigid aromatic monomers (e.g., terephthalic acid, TPA), such as the commercial PBAT, PBST-based aliphatic-aromatic copolyesters. However, the TPA addition severely inhibits the biodegradability of the polyester, content>At 50 mol%, the polymer is difficult to biodegrade. In order to obtain better comprehensive properties (thermal property, mechanical property and biodegradability), the content of terephthalic acid in the commercialized PBAT and PBST aliphatic-aromatic copolyester is generally 40-50 mol%. According to Δ Tm＝ΔHm/ΔSmThe addition of the comonomer destroys the crystallization regularity of the PBS repeating structural unit, reduces the crystallization enthalpy of chain segments or increases the entropy of the chain segments, so that the crystallization capability of PBAT and PBST biodegradable polyester is poor, and the non-woven fabric with better mechanical property and fiber forming property is difficult to prepare by a melt spinning process.
Aiming at the problems, the invention provides a preparation method of high-melting-point fatty biodegradable copolyester by controlling polymerization reaction. The prepared polyester has low aromatic structural unit content and quick and complete biodegradability. Meanwhile, the composite material has higher molecular weight, better mechanical strength and fiber forming performance, is suitable for fiber preparation, and can be further applied to nonwoven materials such as spun-bonded fabrics, hot-air non-woven fabrics and melt-blown fabrics.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and discloses a preparation method of high-melting-point crystalline biodegradable copolyester. In the first stage of the invention, isohexide and dibasic acid or dibasic acid ester are used as reaction monomers, and a biological enzyme low-temperature polymerization reaction or an in-situ acetylation melt polymerization reaction is utilized to obtain an isohexide-based polyester prepolymer (P1). And adding a second aliphatic polyester component (P2) and a chain extender in the second stage to finally obtain the high-melting-point crystalline biodegradable copolyester. The prepared copolyester has complete biodegradability (meaning that a polymer product can be converted into carbon dioxide, water and mineral substances by 100 percent under the action of microorganisms) and better fiber forming performance. The prepared product is suitable for fiber preparation, and can be further applied to nonwoven materials such as spun-bonded, hot-air and melt-blown nonwoven fabrics.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of high-melting-point crystalline biodegradable copolyester is characterized in that isohexide-based polyester prepolymer, aliphatic polyester prepolymer and chain extender are mixed and then react to prepare the high-melting-point crystalline biodegradable copolyester, wherein the isohexide-based polyester prepolymer is prepared by the reaction of isohexide and dibasic acid or dibasic acid ester; the number of carbon atoms continuously connected between two carboxyl functional groups in the dibasic acid is less than or equal to 6; the dibasic acid ester is methyl ester, ethyl ester or divinyl ester corresponding to the dibasic acid; the aliphatic polyester prepolymer is one or more of a PBS prepolymer, a PCL prepolymer, a PIsS prepolymer, a PBST (poly (butylene succinate-co-butylene terephthalate)) prepolymer and a PBAT poly (butylene adipate-co-butylene terephthalate)) prepolymer, and the PIsS prepolymer is a poly (butylene succinate-co-isosorbide succinate) (PBIsS), a poly (propylene succinate-co-isosorbide succinate) (PTIsS) or a poly (ethylene succinate-co-isosorbide succinate) (PEIsS) prepolymer; the mass ratio of the isohexol-based polyester prepolymer to the aliphatic polyester prepolymer is 2: 8-9: 1.
As a preferred technical scheme:
in the preparation method of the high-melting-point crystalline biodegradable copolyester, the number average molecular weight of the isohexide-based polyester prepolymer is 5,000-10,000 g/mol, and the intrinsic viscosity is 0.28-0.45 dL/g.
The preparation method of the high-melting-point crystalline biodegradable copolyester comprises the following steps: mixing biological enzyme, isohexide, dibasic acid or dibasic acid ester under the condition of containing or not containing solvent, and performing enzyme catalytic polymerization to obtain isohexide-based polyester prepolymer;
the solvent is more than one of normal hexane, cyclohexane and toluene; solvents with higher polarity, such as tetrahydrofuran, ethanol, methanol, chloroform and the like, should be avoided as much as possible, and such solvents are relatively easy to cause biological enzyme inactivation, which leads to failure of the enzyme-catalyzed polymerization reaction;
the biological enzyme is lipase;
the molar ratio of the dibasic acid or dibasic ester to the isohexide is 1: 0.95-1.05; when the solvent is contained, the ratio of the dibasic acid or dibasic acid ester to the solvent is 0.2-0.4 mmol/mL; when the biological enzyme contains or does not contain a solvent, the addition amount of the biological enzyme is 5-20% of the sum of the mass addition amounts of the isohexide, the dibasic acid or the dibasic acid ester; the temperature of the enzyme catalytic polymerization reaction is 70-100 ℃, and the time is 50-80 h.
The preparation method of the high-melting-point crystalline biodegradable copolyester is characterized in that the lipase is more than one of immobilized onion pseudocell lipase, immobilized porcine trypsin and immobilized candida antarctica enzyme.
After the enzymatic polymerization reaction is finished, the reaction product is separated and purified by a dissolving-precipitating method (as the solid biological enzyme still exists in the reaction system, the biological enzyme can be filtered out after the generated polymer is dissolved through the dissolving step to achieve the separation purpose), the adopted solvent is chloroform, the precipitator is methanol or ethanol, and the volume ratio of the chloroform to the methanol or the ethanol is 1: 10-50; when the solvent is contained, azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction (the azeotropic distillation ensures that small molecules such as reaction byproducts methanol, ethanol and the like are timely discharged out of the reaction system to promote the forward reaction), and the azeotropic rate during the azeotropic distillation is 0.5-3 mL/min-1100mL of solvent.
The preparation method of the high-melting-point crystalline biodegradable copolyester comprises the following steps: mixing acetic anhydride, a catalyst, isohexide and dibasic acid, and then carrying out in-situ acetylation melt polymerization reaction to obtain an isohexide-based polyester prepolymer;
the catalyst is more than one of dibutyltin oxide, butylstannic acid, stannous octoate, 2-ethyl stannous hexanoate, germanium oxide, antimony trioxide, tetrabutyl titanate and isopropyl titanate;
the molar ratio of acetic anhydride to isohexide is 0.01-0.1: 1, the addition amount of the catalyst relative to dibasic acid is 50-1000 ppm, the molar ratio of the dibasic acid to the isohexide is 1: 0.95-1.05, the temperature of the in-situ acetylation melt polymerization reaction is 110-130 ℃, and the time is 1-2 hours.
In the preparation method of the high-melting-point crystalline biodegradable copolyester, the isohexide is more than one of isomannide, isoidide, isomannide-2, 5-dimethyl alcohol and isoidide-2, 5-dimethyl alcohol;
the dibasic acid is more than one of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, glutaconic acid, traumatic acid, muconic acid, itaconic acid, isomannide-dicarboxylic acid, isoidide-dicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid and a substance C, the chemical molecular formula of the substance C is HOOC- (CHOH) n-COOH, and n is 2, 3 or 4.
In the preparation method of the high-melting-point crystalline biodegradable copolyester, the number average molecular weight of the aliphatic polyester prepolymer is 3,000-30,000 g/mol, and the intrinsic viscosity is 0.19-1 dL/g.
According to the preparation method of the high-melting-point crystalline biodegradable copolyester, the isohexide-based polyester prepolymer, the aliphatic polyester prepolymer and the chain extender are mixed and then subjected to melt polycondensation or reactive extrusion reaction;
the chain extender is more than one of chain extender Joncryl ADR-4368, chain extender SAG-005, chain extender SAG-008, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, 2' -bis (2-oxazoline), 1, 3-phenyl-bis (2-oxazoline), 1, 4-phenyl-bis (2-oxazoline), furan-2, 5-bis (2-oxazoline) and isohexide-2, 5-bis (2-oxazoline);
the molecular end group of the isohexol-based polyester prepolymer (P1) can be hydroxyl or carboxyl (a potentiometric titrator is used for testing the end hydroxyl value and the end carboxyl value), the end hydroxyl value of the hydroxyl end capping is 30-100 mg KOH/g, and the end carboxyl value is 3-15 mg KOH/g; the carboxyl-terminated terminal carboxyl value is 10-100 mg KOH/g; the hydroxyl end group value is 0.23-0.74 mg KOH/g;
the number of the end groups mainly influences the reactivity of subsequent chain extension, and a chain extender capable of reacting with hydroxyl is selected when the hydroxyl is terminated; selecting a chain extender capable of reacting with carboxyl when the carboxyl is terminated; the selection of the chain extender is mainly related to the types of the end groups, the consistency of the types of the end groups of the prepolymer is ensured as much as possible, otherwise, the subsequent molecular weight is difficult to effectively increase;
when the end group of the prepolymer is taken as a hydroxyl group, more than one of a chain extender Joncryl ADR-4368, a chain extender SAG-005, a chain extender SAG-008, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, succinic anhydride, maleic anhydride, phthalic anhydride and pyromellitic anhydride can be selected for carrying out chain extension reaction;
when the end group of the prepolymer is carboxyl, more than one of a chain extender Joncryl ADR-4368, a chain extender SAG-005, a chain extender SAG-008, 2' -bis (2-oxazoline), 1, 3-phenyl-bis (2-oxazoline), 1, 4-phenyl-bis (2-oxazoline), furan-2, 5-bis (2-oxazoline) and isohexide-2, 5-bis (2-oxazoline) can be selected for carrying out chain extension reaction;
the temperature of the melt polycondensation is 140-200 ℃, the time is 0.5-1.5 h, and the vacuum degree is 30-60 Pa; the temperature of the reactive extrusion is 160-220 ℃, and the time is 0.1-0.5 h; the addition amount of the chain extender is 1-2% of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer.
The preparation method of the high-melting-point crystalline biodegradable copolyester is characterized in that the number average molecular weight of the high-melting-point crystalline biodegradable copolyester is 10,000-60,000 g/mol, the intrinsic viscosity is 0.5-1.2 dL/g, and the melting point is 150-190 ℃; the molecular weight of the copolyester may be determined by Gel Permeation Chromatography (GPC) analysis, such as by using a gel permeation chromatograph manufactured by Waters corporation, and measuring with Hexafluoroisopropanol (HFIP) as a mobile phase, at a flow rate of 0.5mL/min and a measuring temperature of 35 ℃, and the final measured molecular weight is calibrated by monodisperse polymethyl methacrylate (PMMA). All sample solutions must be filtered of insoluble particles using a 0.2 μm thick teflon filter before injection into the instrument.
The invention mechanism is as follows:
the high melting point of the copolyester prepared by the invention is because the used isohexide monomer has higher structural rigidity and symmetrical molecular structure, and can be copolymerized with shorter-chain dibasic acid or dibasic acid ester to prepare isohexide-based polyester prepolymer with higher melting point; the copolyester prepared by further chain extension still shows similar high melting point;
the mechanical property of the copolyester prepared by the invention is excellent because the addition of isohexide rigid groups can effectively improve intermolecular force, thereby improving the tensile property of copolyester chips or fibers;
the crystallization performance of the copolyester prepared by the invention is excellent because the repeated structural unit of the isohexide segment in the copolyester has better crystallization, and the crystallization performance of macromolecules can be better maintained by utilizing the chain extender to carry out subsequent chain growth; meanwhile, the repeated structural units of the aliphatic polyester segment in the copolyester also have better crystallinity, so that the macromolecule integrally presents better crystallization property;
the excellent biodegradability of the copolyester prepared by the invention is because the copolyester product contains almost no or only a low content of aromatic terephthalic acid component (depending on the type of aliphatic polyester prepolymer and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer), has a high content of aliphatic chemical structure, and the isohexide as a natural glycosyl derivative is more easily subjected to microbial degradation, so the overall copolyester has excellent biodegradability.
Has the advantages that:
(1) compared with the prior art, the preparation method of the high-melting-point crystalline copolyester has high fat, low aromatic structural unit content and complete biodegradability;
(2) the high-melting-point crystalline copolyester has higher molecular weight and better fiber forming performance, and is suitable for preparing subsequent non-woven materials such as fibers, spun-bonded fabrics, non-woven fabrics and the like.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing n-hexane, bio-enzyme (immobilized onion pseudocell lipase), isohexide (isomannide) and dibasic acid (oxalic acid), and performing enzyme catalytic polymerization reaction (at 80 deg.C for 50 hr) to obtain isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:0.95, the ratio of the dibasic acid to the n-hexane is 0.5mmol/mL, and the addition amount of the biological enzyme is 5% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is methanol, and the volume ratio of the chloroform to the methanol is 1: 10; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 0.5-1.5 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) carrying out reactive blending (at the temperature of 200 ℃ for 0.2h) on an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (PBS prepolymer (0.5dL/g)) and a chain extender (Joncryl ADR-4368) in a double-screw extruder for reaction; wherein the addition amount of the chain extender is 1 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 2: 8;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Comparative example 1
The preparation method of the high-melting-point crystalline biodegradable copolyester basically has the same steps as those in example 1, except that no chain extender is added in comparative example 1. The number average molecular weight of the prepared product is only 6,600g/mol, and the product can not meet the requirement of being used as a high polymer material. The melting point is only 140 ℃ due to the lower molecular weight. The main reason is that the chain extender can provide more functional groups capable of reacting with each other between two chain segments, and better connect high molecular chain segments to form a block copolymer with higher molecular weight, higher melting point and better thermal stability.
Example 2
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing cyclohexane, biological enzyme (immobilized porcine trypsin), isohexide (isomannide) and dibasic acid (malonic acid), and performing enzyme catalytic polymerization (at 90 deg.C for 60 hr) to obtain isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:0.96, the ratio of the dibasic acid to the cyclohexane is 0.6mmol/mL, and the addition amount of the biological enzyme is 6% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is methanol, and the volume ratio of the chloroform to the methanol is 1: 20; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 0.9-2.5 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (PCL prepolymer (0.62dL/g)) and the chain extender (chain extender SAG-005), and then carrying out melt polycondensation (the temperature is 190 ℃ and the time is 0.3h) in a reaction kettle; wherein the addition amount of the chain extender is 1.2 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 3: 7;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 3
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing toluene, biological enzyme (immobilized candida antarctica enzyme), isohexide (isoidide) and dibasic acid (succinic acid), and performing enzyme catalytic polymerization reaction (at 100 ℃ for 70h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:0.97, the ratio of the dibasic acid to the toluene is 0.7mmol/mL, and the addition amount of the biological enzyme is 7% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is methanol, and the volume ratio of the chloroform to the methanol is 1: 30; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 1.2-2.5 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) performing reactive blending (the temperature is 180 ℃, and the time is 0.5h) on the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (PIsS prepolymer (0.36dL/g)) and the chain extender (chain extender SAG-008) in a double-screw extruder to react; wherein the addition amount of the chain extender is 1.5 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 4: 6;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Comparative example 2
A preparation method of high-melting-point crystalline biodegradable copolyester, which has the steps basically the same as those in example 3, except that isoidide in example 3 is replaced by 1, 4-butanediol; the melting point of the prepared copolyester product is 115 ℃;
comparing comparative example 2 with example 3, it can be seen that the melting point of the copolyester of example 3 is higher because of the long carbon chain length of 1, 4-butanediol, the high structural flexibility and the lower melting point of the prepolymer prepared.
Comparative example 3
The preparation method of the high-melting-point crystalline biodegradable copolyester is basically the same as that in example 3, except that succinic acid in example 3 is replaced by sebacic acid; the melting point of the prepared copolyester product is 85 ℃;
comparing comparative example 3 with example 3, it can be seen that the melting point of the copolyester of example 3 is higher because the melting point of the prepared pre-polyester is lower due to the long carbon chain of sebacic acid, the high structural flexibility.
Comparative example 4
A preparation method of high-melting-point crystalline biodegradable copolyester, which basically has the same steps as those in example 3, and is different from the steps that the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer in example 3 is replaced by 1:9, namely 4: 6; the enthalpy of crystallization of the prepared copolyester product is 10.0J/g;
comparing comparative example 4 with example 3, it can be seen that the enthalpy of crystallization of the copolyester in example 3 is higher because the crystallinity of the aliphatic polyester prepolymer PIsS is low, the amount of the isohexide-based polyester prepolymer added is too low, and although the finally prepared copolyester has a melting point, the enthalpy of crystallization is too low, it is difficult to prepare subsequent fibers, and the fiber forming property is poor.
Example 4
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing cyclohexane/toluene (volume ratio of 6:1), biological enzyme (immobilized onion pseudocell lipase and immobilized pig trypsin in a mass ratio of 1: 1), isohexide (isoidide) and dibasic acid (glutaric acid), and performing enzyme catalytic polymerization reaction (at 85 ℃ for 80h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:0.98, the ratio of the dibasic acid to the cyclohexane/toluene is 0.8mmol/mL, and the addition amount of the biological enzyme is 8% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is methanol, and the volume ratio of the chloroform to the methanol is 1: 40; performing azeotropic distillation in the process of the enzyme-catalyzed polymerization reaction, wherein the azeotropic rate in the azeotropic distillation is 2.3-3.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) mixing an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (PBST prepolymer (0.51dL/g)) and a chain extender (2, 2' -bis (2-oxazoline)), and then carrying out melt polycondensation (the temperature is 160 ℃ and the time is 0.3h) in a reaction kettle; wherein the addition amount of the chain extender is 1.3 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 5: 5;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 5
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing a solvent (same as example 1), biological enzymes (immobilized onion pseudocell lipase and immobilized candida antarctica enzyme in a mass ratio of 1: 1), isohexide (isomannide-2, 5-dimethanol) and dibasic acid (adipic acid), and carrying out enzyme catalytic polymerization reaction (at the temperature of 95 ℃ for 55 hours) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:0.98, the ratio of the dibasic acid to the solvent is 0.9mmol/mL, and the addition amount of the biological enzyme is 9% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is methanol, and the volume ratio of the chloroform to the methanol is 1: 50; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 2.5-3.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) reacting an isohexide-based polyester prepolymer (prepared in step (1)), an aliphatic polyester prepolymer (PBAT prepolymer (0.48dL/g)) and a chain extender (1, 3-phenyl-bis (2-oxazoline)) in a double-screw extruder at a temperature of 150 ℃ for 0.4 h; wherein the addition amount of the chain extender is 1.8 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 6: 4;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 6
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing a solvent (same as example 2), a biological enzyme (same as example 1), isohexide (isoidide-2, 5-dimethanol) and dibasic acid (adipic acid), and performing enzyme catalytic polymerization (at 90 ℃ for 65h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:1.02, the ratio of the dibasic acid to the solvent is 1mmol/mL, and the addition amount of the biological enzyme is 10% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is methanol, and the volume ratio of the chloroform to the methanol is 1: 15; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 1.0-2.0 mL/min-1100mL of solvent (rate of distilling off by-products)Not constant, controlled within a fluctuation range during the test);
(3) carrying out reactive blending (at the temperature of 140 ℃ and for 0.5h) on an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (PBS (0.55dL/g) and PCL (0.61dL/g) in a mass ratio of 1: 1) and a chain extender (hexamethylene diisocyanate) in a double-screw extruder for reaction; wherein the addition amount of the chain extender is 2% of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 7: 3;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 7
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing a solvent (same as example 3), a biological enzyme (same as example 2), isomannide (isomannide and isoidide in a mass ratio of 1: 1) and dibasic acid (maleic acid), and carrying out enzyme catalytic polymerization reaction (at the temperature of 95 ℃ for 75 hours) to obtain an isohexol-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:1.03, the ratio of the dibasic acid to the solvent is 0.55mmol/mL, and the addition amount of the biological enzyme is 11% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying the reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is ethanol, and the volume ratio of the chloroform to the ethanol is 1: 25; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 1.0-2.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) carrying out reactive blending (at the temperature of 170 ℃ and the time of 0.4h) on an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (same as the example 1) and a chain extender (1, 5-naphthalene diisocyanate) in a double-screw extruder to react; wherein the addition amount of the chain extender is 1.6 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 8: 2;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 8
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing a solvent (same as example 4), a biological enzyme (same as example 3), isohexide (isomannide-2, 5-dimethyl alcohol and isoidide-2, 5-dimethyl alcohol in a mass ratio of 1: 1) and dibasic acid (fumaric acid), and carrying out enzyme catalytic polymerization reaction (at the temperature of 95 ℃ for 80 hours) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:1.04, the ratio of the dibasic acid to the solvent is 0.65mmol/mL, and the addition amount of the biological enzyme is 12% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is ethanol, and the volume ratio of the chloroform to the ethanol is 1: 35; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 1.0-2.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) carrying out reactive blending (at the temperature of 150 ℃ and the time of 0.2h) on an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (same as the example 2) and a chain extender (diphenylmethane diisocyanate) in a double-screw extruder to react; wherein the addition amount of the chain extender is 1.7 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 9: 1;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 9
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing a solvent (same as example 1), a biological enzyme (same as example 4), isohexide (isomannide, isomannide-2, 5-dimethyl alcohol, isoidide-2, 5-dimethyl alcohol and diacid (glutaconic acid) in a mass ratio of 1:1: 1), and carrying out enzyme catalytic polymerization reaction (the temperature is 95 ℃ and the time is 80 hours) to prepare an isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:1.05, the ratio of the dibasic acid to the solvent is 0.75mmol/mL, and the addition amount of the biological enzyme is 13% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is ethanol, and the volume ratio of the chloroform to the ethanol is 1: 45; when the solvent is contained, azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate in the azeotropic distillation is 1.0-2.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (same as the example 3) and a chain extender (isophorone diisocyanate), and then carrying out melt polycondensation (the temperature is 180 ℃ and the time is 0.3h) in a reaction kettle; wherein the addition amount of the chain extender is 1.5 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 2: 8;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 10
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing solvent (same as example 2), biological enzyme (same as example 5), isohexide (same as example 7) and dibasic acid (traumatic acid), and performing enzyme-catalyzed polymerization at 85 deg.C for 80 hr to obtain isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:1.03, the ratio of the dibasic acid to the solvent is 0.85mmol/mL, and the addition amount of the biological enzyme is 14% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying the reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is ethanol, and the volume ratio of the chloroform to the ethanol is 1: 38; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 1.0-3.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) carrying out reactive blending (at the temperature of 160 ℃ and for 0.5h) on an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (same as the example 4) and a chain extender (succinic anhydride) in a double-screw extruder; wherein the addition amount of the chain extender is 1.9 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 3: 7;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 11
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) an isohexol-based polyester prepolymer was prepared by mixing a solvent (same as in example 3), a biological enzyme (same as in example 1), isohexide (same as in example 8), and a dibasic acid (muconic acid) and then subjecting the mixture to an enzymatic polymerization reaction (at a temperature of 95 ℃ for 72 hours); wherein the molar ratio of the dibasic acid to the isohexide is 1:1.04, the ratio of the dibasic acid to the solvent is 0.95mmol/mL, and the addition amount of the biological enzyme is 20% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying the reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is ethanol, and the volume ratio of the chloroform to the ethanol is 1: 25; azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate during the azeotropic distillation is 1.0-2.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) carrying out reactive blending (at the temperature of 170 ℃ and for 0.5h) on an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (same as the example 5) and a chain extender (maleic anhydride) in a double-screw extruder; wherein the addition amount of the chain extender is 2% of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 3: 7;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 12
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (dibutyltin oxide), isohexide (same as in example 1) and dibasic acid (itaconic acid), and carrying out in-situ acetylation melt polymerization (at the temperature of 110 ℃ for 1h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.2:1, the addition amount of the catalyst relative to other monomers is 200ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.01;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (same as the aliphatic polyester prepolymer in the example 1) and a chain extender (phthalic anhydride), and then carrying out reactive extrusion (at the temperature of 170 ℃ for 0.1h) reaction; wherein the addition amount of the chain extender is 2% of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 3: 7;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 13
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (butylstannoic acid), isohexide (same as example 2) and dibasic acid (malonic acid), and carrying out in-situ acetylation melt polymerization reaction (at 120 ℃ for 1.5h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.3:1, the addition amount of the catalyst relative to other monomers is 300ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.03;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (same as the example 2) and a chain extender (pyromellitic dianhydride), and then carrying out reactive extrusion (the temperature is 180 ℃ and the time is 0.2h) reaction; wherein the addition amount of the chain extender is 1.5 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 4: 6;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 14
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (stannous octoate), isohexide (same as example 3) and dibasic acid (isomannide-dicarboxylic acid), and then carrying out in-situ acetylation melt polymerization reaction (at the temperature of 130 ℃ for 1.5h) to prepare an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.4:1, the addition amount of the catalyst relative to other monomers is 400ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.05;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (same as the aliphatic polyester prepolymer in the example 3) and the chain extender (2, 2' -bis (2-oxazoline)) and then carrying out reactive extrusion (the temperature is 190 ℃ and the time is 0.3h) reaction; wherein the addition amount of the chain extender is 1.7 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 5: 5;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 15
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (2-stannous ethyl hexanoate), isohexide (same as example 4) and dibasic acid (isoidide-dicarboxylic acid), and then carrying out in-situ acetylation melt polymerization reaction (the temperature is 120 ℃, and the time is 1h) to prepare an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.5:1, the addition amount of the catalyst relative to other monomers is 500ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.04;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (same as the example 4) and the chain extender (1, 3-phenyl-bis (2-oxazoline)) and then carrying out reactive extrusion (at the temperature of 200 ℃ for 0.4h) reaction; wherein the addition amount of the chain extender is 1.8 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 6: 4;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 16
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (germanium oxide), isohexide (same as in example 5) and dibasic acid (1, 4-cyclohexanedicarboxylic acid), and carrying out in-situ acetylation melt polymerization reaction (at 120 ℃ for 1h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.25:1, the addition amount of the catalyst relative to other monomers is 500ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.03;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (same as the example 5) and the chain extender (1, 4-phenyl-bis (2-oxazoline)) and then carrying out reactive extrusion (at the temperature of 210 ℃ for 0.5h) reaction; wherein the addition amount of the chain extender is 1.6 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 7: 3;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 17
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (antimony trioxide), isohexide (same as in example 6) and a dibasic acid (succinic acid), and carrying out in-situ acetylation melt polymerization (at the temperature of 120 ℃ for 2 hours) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.35:1, the addition amount of the catalyst relative to other monomers is 600ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.03;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (prepared in the same way as in the example 6) and the chain extender (furan-2, 5-bis (2-oxazoline)) and then carrying out reactive extrusion (the temperature is 220 ℃ and the time is 0.15h) reaction; wherein the addition amount of the chain extender is 1.3 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 8: 2;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 18
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (tetrabutyl titanate), isohexide (same as in example 7) and dibasic acid (glutaric acid), and carrying out in-situ acetylation melt polymerization reaction (at the temperature of 125 ℃ for 1h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.45:1, the addition amount of the catalyst relative to other monomers is 800ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.03;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing an isohexide-based polyester prepolymer (prepared in step (1)), an aliphatic polyester prepolymer (prepared in the same way as in example 1) and a chain extender (isohexide-2, 5-bis (2-oxazoline)) and then carrying out reactive extrusion (at the temperature of 160 ℃ for 0.1h) reaction; wherein the addition amount of the chain extender is 2% of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 9: 1;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 19
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing acetic anhydride, a catalyst (isopropyl titanate), isohexide (same as in example 8) and dibasic acid (adipic acid), and carrying out in-situ acetylation melt polymerization reaction (at the temperature of 120 ℃ for 2h) to obtain an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.3:1, the addition amount of the catalyst relative to other monomers is 600ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.02;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (same as the aliphatic polyester prepolymer in the example 2) and a chain extender (2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate in a mass ratio of 1: 1), and then carrying out reactive extrusion (at the temperature of 160 ℃ for 0.1h) reaction; wherein the addition amount of the chain extender is 1 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 2: 8;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Example 20
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) acetic anhydride, catalyst (germanium oxide and tetrabutyl titanate in a mass ratio of 1: 1), isohexide (same as in example 9), dibasic acid (substance C, chemical formula HOOC- (CHOH)2mixing-COOH) and then carrying out in-situ acetylation melt polymerization reaction (at the temperature of 125 ℃ for 2 hours) to prepare an isohexide-based polyester prepolymer; wherein the molar ratio of acetic anhydride to isohexide is 0.3:1, the addition amount of the catalyst relative to other monomers is 300ppm, and the molar ratio of the dibasic acid to the isohexide is 1: 1.03;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) mixing the isohexide-based polyester prepolymer (prepared in the step (1)), the aliphatic polyester prepolymer (same as the example 3) and the chain extender (same as the example 12), and then carrying out reactive extrusion (at the temperature of 160 ℃ for 0.1 h); wherein the addition amount of the chain extender is 1.2 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 3: 7;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
Examples 21 to 25
A preparation method of high-melting-point crystalline biodegradable copolyester, which comprises the steps basically the same as those in example 3, except that dibasic acid is replaced by the substances in table 1, and the performance indexes of the prepared isohexide-based polyester prepolymer are shown in table 2; and the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
TABLE 1
Figure GDA0003018190970000151
Example 26
A preparation method of high-melting-point crystalline biodegradable copolyester comprises the following steps:
(1) mixing biological enzyme (same as example 3), isohexide (same as example 7) and dibasic acid (succinic acid), and performing enzyme catalytic polymerization reaction (at 90 deg.C for 90 hr) to obtain isohexide-based polyester prepolymer; wherein the molar ratio of the dibasic acid to the isohexide is 1:1.04, the ratio of the dibasic acid to the solvent is 0.8mmol/mL, and the addition amount of the biological enzyme is 10% of the sum of the mass addition amounts of the isohexide and the dibasic acid;
the number average molecular weight and the intrinsic viscosity of the obtained isohexide-based polyester prepolymer are shown in Table 2;
(2) separating and purifying a reaction product by a dissolving-precipitating method, wherein the adopted solvent is chloroform, the precipitating agent is methanol, and the volume ratio of the chloroform to the methanol is 1: 50; when the solvent is contained, azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate in the azeotropic distillation is 2.5-3.0 mL/min-1100mL of solvent (the rate of evaporating the by-product is not constant and is controlled within a fluctuation range during the test);
(3) mixing an isohexide-based polyester prepolymer (prepared in the step (1)), an aliphatic polyester prepolymer (PBAT prepolymer (0.48dL/g)) and a chain extender (1, 3-phenyl-bis (2-oxazoline)), and then carrying out melt polycondensation (the temperature is 150 ℃ and the time is 0.4h) in a reaction kettle; wherein the addition amount of the chain extender is 1.8 percent of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer, and the mass ratio of the isohexide-based polyester prepolymer to the aliphatic polyester prepolymer is 6: 4;
the performance indexes of the high-melting-point crystalline biodegradable copolyester are shown in table 2.
TABLE 2 number average molecular weight and intrinsic viscosity of isohexide-based polyester prepolymers and final products
Figure GDA0003018190970000161
Figure GDA0003018190970000171

Claims (7)

1. A preparation method of high-melting-point crystalline biodegradable copolyester is characterized by comprising the following steps: mixing isohexide-based polyester prepolymer, aliphatic polyester prepolymer and chain extender, and reacting to obtain high-melting-point crystalline biodegradable copolyester, wherein the isohexide-based polyester prepolymer is prepared by reacting isohexide with dibasic acid or dibasic acid ester, or is prepared by mixing acetic anhydride, a catalyst, isohexide and dibasic acid and then carrying out in-situ acetylation melt polymerization reaction; the number of carbon atoms continuously connected between two carboxyl functional groups in the dibasic acid is less than or equal to 6; the dibasic acid ester is methyl ester, ethyl ester or divinyl ester corresponding to the dibasic acid; the aliphatic polyester prepolymer is one or more of a PBS prepolymer, a PIsS prepolymer, a PBST prepolymer and a PBAT prepolymer; the mass ratio of the isohexol-based polyester prepolymer to the aliphatic polyester prepolymer is 2: 8-9: 1;
the PIsS prepolymer is a poly (butylene succinate-co-isosorbide succinate), poly (propylene succinate-co-isosorbide succinate) or poly (ethylene succinate-co-isosorbide succinate) prepolymer;
the isohexide is one or more of isomannide, isoidide, isomannide-2, 5-dimethyl alcohol and isoidide-2, 5-dimethyl alcohol;
the number average molecular weight of the isohexol-based polyester prepolymer is 5,000-10,000 g/mol, and the intrinsic viscosity is 0.28-0.45 dL/g;
the number average molecular weight range of the aliphatic polyester prepolymer is 3,000-30,000 g/mol, and the intrinsic viscosity is 0.19-1 dL/g;
the high-melting-point crystalline biodegradable copolyester has the number average molecular weight of 10,000-60,000 g/mol, the intrinsic viscosity of 0.5-1.2 dL/g and the melting point of 150-190 ℃.
2. The method for preparing high melting point crystalline biodegradable copolyester according to claim 1, wherein the preparation process of the isohexol-based polyester prepolymer is as follows: mixing biological enzyme, isohexide, dibasic acid or dibasic acid ester under the condition of containing or not containing solvent, and performing enzyme catalytic polymerization to obtain isohexide-based polyester prepolymer;
the solvent is more than one of normal hexane, cyclohexane and toluene;
the biological enzyme is lipase;
the molar ratio of the dibasic acid or dibasic ester to the isohexide is 1: 0.95-1.05; when the solvent is contained, the ratio of the dibasic acid or dibasic acid ester to the solvent is 0.2-0.4 mmol/mL; when the biological enzyme contains or does not contain a solvent, the addition amount of the biological enzyme is 5-20% of the sum of the mass addition amounts of the isohexide, the dibasic acid or the dibasic acid ester; the temperature of the enzyme catalytic polymerization reaction is 70-100 ℃, and the time is 50-80 h.
3. The method for preparing high melting point crystalline biodegradable copolyester according to claim 2, wherein the lipase is one or more of immobilized onion pseudocell lipase, immobilized porcine trypsin and immobilized candida antarctica enzyme.
4. The preparation method of high-melting-point crystalline biodegradable copolyester as claimed in claim 2, wherein after the enzymatic polymerization reaction is finished, the reaction product is further separated and purified by a dissolution-precipitation method, the adopted solvent is chloroform, the precipitant is methanol or ethanol, and the volume ratio of chloroform to methanol or ethanol is 1: 10-50; when the solvent is contained, azeotropic distillation is also carried out in the process of the enzyme-catalyzed polymerization reaction, and the azeotropic rate in the azeotropic distillation is 0.5-3 mL/min-1100mL of solvent.
5. The method for preparing high melting point crystalline biodegradable copolyester according to claim 1, wherein the preparation process of the isohexol-based polyester prepolymer is as follows: mixing acetic anhydride, a catalyst, isohexide and dibasic acid, and then carrying out in-situ acetylation melt polymerization reaction to obtain an isohexide-based polyester prepolymer;
the catalyst is more than one of dibutyltin oxide, butylstannic acid, stannous octoate, germanium oxide, antimony trioxide, tetrabutyl titanate and isopropyl titanate;
the molar ratio of acetic anhydride to isohexide is 0.01-0.1: 1, the addition amount of the catalyst relative to dibasic acid is 50-1000 ppm, the molar ratio of the dibasic acid to the isohexide is 1: 0.95-1.05, the temperature of the in-situ acetylation melt polymerization reaction is 110-130 ℃, and the time is 1-2 hours.
6. The method for preparing high-melting-point crystalline biodegradable copolyester according to any one of claims 2-5, wherein the dibasic acid is one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, glutaconic acid, muconic acid, itaconic acid, isomannide-dicarboxylic acid, isoidide-dicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid and a substance C, the chemical formula of the substance C is HOOC- (CHOH) n-COOH, and n is 2, 3 or 4.
7. The method for preparing high melting point crystalline biodegradable copolyester according to claim 1, wherein the isohexol-based polyester prepolymer, the aliphatic polyester prepolymer and the chain extender are mixed and then subjected to melt polycondensation or reactive extrusion reaction;
the chain extender is more than one of chain extender JoncrylADR-4368, chain extender SAG-005, chain extender SAG-008, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, 2' -bis (2-oxazoline), 1, 3-phenyl-bis (2-oxazoline), 1, 4-phenyl-bis (2-oxazoline), furan-2, 5-bis (2-oxazoline) and isohexide-2, 5-bis (2-oxazoline);
the temperature of the melt polycondensation is 140-200 ℃, the time is 0.5-1.5 h, and the vacuum degree is 30-60 Pa; the temperature of the reactive extrusion is 160-220 ℃, and the time is 0.5-1.5 h; the addition amount of the chain extender is 1-2% of the total mass of the isohexide-based polyester prepolymer and the aliphatic polyester prepolymer.
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